Enhancing Polysulfide Confinement and Electrochemical Kinetics by Amorphous Cobalt Phosphide for Highly Efficient...

The application of lithium-sulfur (Li-S) batteries is severely hampered by the shuttle effect and sluggish redox kinetics. Herein, amorphous cobalt phosphide grown on a reduced graphene oxide-multiwalled carbon nanotube (rGO-CNT-CoP(A)) is designed as the sulfur host to conquer the above bottlenecks. The differences between amorphous cobalt phosphide (CoP) and crystalline CoP on the surface adsorption as well as conversion of lithium polysulfides (LiPSs) are investigated by systematical experiments and density-functional theory (DFT) calculations. Specifically, the amorphous CoP not only strengthens the chemical adsorption to LiPSs but also greatly accelerates liquid-phase conversions of LiPSs as well as the nucleation and growth of Li₂S. DFT calculation reveals that the amorphous CoP possesses higher binding energies and lower diffusion energy barriers for LiPSs. In addition, the amorphous CoP features reduced energy gap and the increased electronic concentrations of adsorbed LiPSs near Fermi level. These characteristics contribute to the enhanced chemisorption ability and the accelerated redox kinetics. Simultaneously, the prepared S/rGO-CNT-CoP(A) electrode delivers an impressive initial capacity of 872 mAh g^-1 at 2 C and 617 mAh g^-1 can be obtained after 200 cycles, exhibiting excellent cycling stability. Especially, it achieves outstanding electrochemical performance even under high sulfur loading (5.3 mg cm^-2) and lean electrolyte (E/S = 7 μL_E mg^-1_S) conditions. This work exploits the application potential for amorphous materials and contributes to the development of highly efficient Li-S batteries.